Electrolyte and process for depositing a matt metal layer

ABSTRACT

An electrolytic composition for the deposition of a matt metal layer onto a substrate and deposition process where the composition comprises a source of metal from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, In, Sn, Sb, Re, Pt, Au, Bi, and combinations thereof; 
     a substituted or unsubstituted polyalkylene oxide or its derivative as an emulsion and/or dispersion former; and a compound comprising fluorated or perfluorated hydrophobic chains or which is a polyalkylene oxide substituted quaternary ammonium compound as wetting agent; wherein the electrolytic composition forms a microemulsion and/or dispersion.

REFERENCE TO RELATED CASE

This application is a continuation of U.S. Ser. No. 12/168,680, filed Jul. 7, 2008, issued Jun. 5, 2012 as U.S. Pat. No. 8,192,607, which is a continuation-in-part of international application PCT/EP2006/000076, filed 6 Jan. 2006, the entire disclosure of which is hereby incorporated by reference.

FIELD OF THE INVENTION

The present invention relates to an electrolyte and to a process for depositing a matt metal layer on a substrate from an electrolyte comprising an emulsion and/or dispersion former or a wetting agent.

BACKGROUND OF THE INVENTION

In the production of metallic layers on substrates the aim generally is to obtain preferably smooth and high gloss coats. But depending on the specific application, it is frequently desired to obtain a metal coat which is not glossy but matt. The reason for that may be the optical appearance of this coat, and also the technical properties, i.e. the nonglaring of such coats. Fields of application for matt deposited metal layers on substrates are for instance the jewelry industry, fittings industry, automobile industry, but also the optical and precision industry, where especially the nonglaring of these coats is important. From prior art matt deposited nickel or nickel alloy layers as well as cobalt layers are known. While the deposition of such potentially allergy-causing metals is noncritical in many fields, it is desirable to avoid these metals in the field of the jewelry industry or also in the field of kitchenware and kitchen utensils. Within the field of the optical or precision industries the deposition of matt metal layers of the most different metals is desirable because of the different properties of the respective metals. In addition, it is desirable to be able to adjust the degree of mattness of the deposited metal layer over a vast range. It is an object of the present invention to provide an electrolyte as well as a process for depositing matt metal layers on substrates, by which method a variety of metals can be deposited with different degrees of mattness on the most different substrates.

Briefly, therefore, the invention is directed to an electrolytic composition for the deposition of a matt metal layer onto a substrate and deposition process where the composition comprises a source of metal from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, In, Sn, Sb, Re, Pt, Au, Bi, and combinations thereof; a substituted or unsubstituted polyalkylene oxide or its derivative as an emulsion and/or dispersion former; and a compound comprising fluorated or perfluorated hydrophobic chains or which is a polyalkylene oxide substituted quaternary ammonium compound as wetting agent; wherein the electrolytic composition forms a microemulsion and/or dispersion.

Other objects and features of the invention will be in part apparent and in part pointed out hereinafter.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The objects of the invention are achieved by an electrolyte for depositing a matt metal layer on a substrate from an electrolyte comprising an emulsion and/or dispersion former or a wetting agent, characterized in that the electrolyte includes for a metal to be deposited a metal from the group consisting of Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, W, Re, Pt, Au, Tl, Pb, Bi, preferably from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, In, Sn, Sb, Re, Pt, Au, Bi, or an alloy of these metals, that the emulsion and/or dispersion former is a substituted or unsubstituted polyalkylene oxide or its derivative, that the wetting agent includes fluorated or perfluorated hydrophobic chains or is a polyalkylene oxide substituted quaternary ammonium compound, and that the electrolyte, emulsion and/or dispersion formers or wetting agents form a microemulsion and/or dispersion.

Concerning the process, the object is solved by a process for electrolytically depositing a matt metal layer on a substrate, wherein the substrate is connected with a voltage source in a galvanizing bath that comprises an electrolyte according to the invention and a counter electrode, and a current which is suitable for depositing a metal layer on the substrate is applied between the substrate and the counter electrode.

It has been discovered that the formation of microemulsions in electrolytes is suitable for the matt deposition of the most different metals from the corresponding electrolytes. Further, it has been discovered that for the formation of these microemulsions in electrolytes of most different metals to be deposited both polyalkyleneglycols or their derivatives, wetting agents with fluorated or perfluorated hydrophobic chains, and quaternary ammonium compounds substituted by polyalkylene oxide chains are suited. These compounds can be used in a vast range for the production of emulsions in electrolytes of the most different metals and they can be used individually.

If polyalkyleneglycols are used for the emulsion and/or dispersion formers, especially polymers with different percentages of hydrophilic and hydrophobic structures, preferably consisting of polyethylene and polypropylene glycols turned out to be suitable in addition to homogeneously structured polymers. In this case it is among others the percentage of hydrophilic and hydrophobic structures which is decisive for the degree of mattness of the deposited metal layer in dependence of the average molecular weight, wherein average molecular weights >200 g/mol, for polymers with a high percentage of hydrophobic structures preferably 200 to 2000 g/mol, and for polymers with a high percentage of hydrophilic structures even more preferably >4000/mol are generally suited.

At the use of fluorated or perfluorated wetting agents, wetting agents of the general formula

R^(f)CH₂CH₂O(CH₂CH₂O)_(x)H  (formula 1)

with R^(f)=F(CF₂CF₂)_(n), wherein X=6 to 15 and n=2 to 10, are particularly suited. The average molecular weight of the fluorated or perfluorated wetting agents is, according to the invention, between about 550 and about 1000 g/mol, preferably between about 700 and about 1000 g/mol. In this case, too the average molecular weight has an influence on the degree of mattness.

Another type of wetting agent suitable for the deposition of metal layers from electrolytes in accordance with the invention is polyalkylene oxide-substituted quaternary ammonium compounds preferably following the general formula

wherein at least one radical R¹, R², R³ or R⁴ is a polyalkylene oxide substituent and the remaining radicals independently are same or different straight-chained or branched saturated or unsaturated C₁ to C₁₈ alkyl chains and X⁻ is a halide, a sulfate anion or anion of a C₁ to C₆ carboxylic acid. It turned out that especially quaternary ammonium compounds of the general formula 2 are suited, in which R¹ and R² are a C₈ to C₁₂, preferably a C₁₀ alkyl side chain, R³ is a C₁ to C₃, preferably a C₁ alkyl side chain, R⁴ corresponds to the general formula [CH₂—CH₂—O]_(n)H with n=1 to 5, and X⁻ is the anion of a C₂ to C₄ carboxylic acid.

The average molecular weight of the quaternary ammonium compound which is added to the electrolyte, in accordance with the invention, is between about 200 to about 1000 g/mol, preferably between 400 and about 500 g/mol and even more preferably between about 450 and about 460 g/mol.

Additionally it turned out that the addition of polytetrafluorethylene particles to the electrolyte according to the invention has an influence on the properties of the deposited matt metal layers. Accordingly, in the deposition of matt metal layers from electrolytes according to the invention which additionally contain polytetrafluorethylene particles a surface appears which is considerably softer concerning tactility and which even exhibits a clearly lower susceptibility to finger prints (touch free) compared to matt surfaces which have been deposited from electrolytes according to the invention without the addition of polytetrafluorethylene particles.

It has been discovered that the medium particle diameter of the added polytetrafluorethylene particles should be within a range of about 10 to about 1000 nm, preferably about 100 to about 300 nm.

According to the invention, the polytetrafluorethylene particles can be added at a concentration between about 0.1 and 1000 mg/l, preferably between about 0.5 and 5 mg/l.

The preferred deposition parameters include a working temperature between 50 and 55° C., a current density between about 3 and about 7 A/dm², and an exposure time of the substrate to the electrolyte of between about 5 and about 20 minutes.

The following examples show embodiments of the electrolyte according to the invention as well as of the process according to the invention, but the invention cannot be limited to these exemplary embodiments.

Example 1

A Cu electrolyte having the following composition:

55 g/l Cu²⁺ 66 g/l H₂SO₄

100 mg/l Cl⁻ 200 mg/l bis-(3-sulfopropyl)-disulfide, disodium salt are mixed with 2 g/l polypropyleneglycol having a molar mass of 900 g/mol. Galvanizing takes places on an angular sheet for 10 minutes at 5 A/dm² and 35° C., with the cathode being moved 2 m/min. Air movement is not required. Surprisingly, a uniform pearlescent effect is obtained in the high and low current density region. Because of the minimum amount of organic brighteners, there are no adherence problems during a current interruption and thereafter adhering layers can be deposited from an acidic bronze electrolyte or from a trivalent chromium electrolyte. The degree of mattness of the pearlescent effect can be controlled through the concentration of the polymer. By a single filtering over Celite all of the pearlescent brightener is removed.

Example 2

When using the parameters described in example 1, a stable and uniform pearlescent effect is obtained at 26° C. and with the addition of 300 mg/l of a polyalkyleneglycol having the following block polymer structure instead of the polypropyleneglycole described in example 1:

HO—(CH₂—CH₂—O)_(x)—(CH₂—CH(CH₃)—O)_(y)—(CH₂—CH₂—O)_(z)—H

The average molecular weight amounts to 1700 g/mol, with the polyethylene oxide fraction (x+z) being 20% of the molecular mass.

Example 3

In a bronze electrolyte having the following composition:

12 g/l Cu(II) 2 g/l Sn(II)

100 g/l methanesulfonic acid 2 g/l hydrochinone there is also obtained a uniform pearlescent effect with 5 mg/l polyalkyleneglycol having the block polymer structure shown in example 2 with a molecular mass of 5000 g/mol and a fraction of 20% of polyethylene oxide at a current density of 2 A/dm², 25° C. and a cathode movement of 1 m/min.

Example 4

In a Watts electrolyte having the following composition:

440 g/l nickel sulfate 30 g/l boric acid 40 g/l nickel chloride 5 g/l sodium saccharinate a uniform matt effect is obtained after 10 minutes at a temperature of 52° C., a pH value of 4.2, a current density of 5 A/dm² and a cathode movement of 2 m/min, through the addition of 10 mg/l of the following CF-substituted polyethyleneglycol having an average molecular weight of 700 g/mol and denoted as a wetting agent, with the main component being characterized by X=5 and Y=10,

F—(CF₂—CF₂)_(x)—(CH₂—CH₂—O)_(y)—H.

Example 5

If in example 4 the CF₂-substituted polyethyleneglycol is replaced by polyethyleneglycol substituted ammonium compounds, a uniform mattness effect is obtained having a different structure than in example 4. For instance, a nickel-plated brass sheet with a pearlescent effect can be obtained by the addition of 8 mg/l didecylmethylpoly-(oxethyl)ammonium propionate in a Watts electrolyte analogously with example 4.

Example 6

The emulsion of polyethyleneglycol-substituted ammonium salt produced in example was added 1 ml/l PTFE suspension (Zonyl TE3667-N, Dupont), whereby different structures and properties of the layers were obtained. The surfaces thus produced exhibit a strongly hydrophobic dirt-repellent effect. 

1. An electrolytic composition for the deposition of a Ni-free matt metal layer onto a substrate, the composition comprising: a) a source of metal selected from the group consisting of Cr, Mn, Fe, Co, Cu, Zn, Ru, Rh, Pd, Ag, In, Sn, Sb, Re, Pt, Au, and Bi and combinations thereof; b) an emulsion and/or dispersion former comprising a substituted or unsubstituted polyalkylene oxide or its derivative; c) a wetting agent selected from the group consisting of a compound comprising i) a fluorinated or perfluorinated hydrophobic chain, OR ii) a polyalkylene oxide substituted quaternary ammonium compound, OR iii) a combination thereof; and d) polytetrafluorethylene particles with an average particle diameter of about 10 nm to about 1000 nm; wherein the electrolytic composition forms a microemulsion and/or dispersion.
 2. The electrolyte composition of claim 1 wherein the source of metal is Cu.
 3. The electrolyte composition of claim 1 wherein the source of metal is Sn and Co.
 4. The electrolyte composition of claim 1 wherein the source of metal is Ag.
 5. The electrolyte composition of claim 1 wherein the emulsion and/or dispersion former is selected from the group consisting of a substituted or unsubstituted polyethylene oxide, polypropylene oxide, polypropylene-polyethylene oxide block copolymer, and a mixture thereof.
 6. The electrolyte composition of claim 5 wherein the emulsion and/or dispersion former has an average molecular weight >200 g/mol.
 7. The electrolyte composition of claim 5 wherein the emulsion and/or dispersion former compound has a high percentage of hydrophobic structures and a molecular weight between about 200 and about 2000 g/mol.
 8. The electrolyte composition of claim 5 wherein the emulsion and/or dispersion former has a high percentage of hydrophilic structures and a molecular weight >4000 g/mol.
 9. The electrolyte composition of claim 1 wherein the fluorated or perfluorated wetting agent has the general formula R^(f)CH₂CH₂O(CH₂CH₂O)_(x)H with R^(f)=F(CF₂CF₂)_(n), wherein X=6 to 15 and n=2 to
 10. 10. The electrolyte composition of claim 9 wherein the average molecular weight of the wetting agent is between about 550 and about 1000 g/mol.
 11. The electrolyte composition of claim 9 wherein the average molecular weight of the wetting agent is between about 700 and about 1000 g/mol.
 12. The electrolyte composition of claim 1 wherein the wetting agent is a polyalkylene oxide-substituted quaternary ammonium compound which has the following general formula

wherein at least one radical R¹, R², R³ or R⁴ is a polyalkylene oxide substituent and the remaining radicals independently are same or different straight-chained or branched saturated or unsaturated C₁ to C₁₈ alkyl chains and X⁻ is a halide, a sulfate anion or anion of a C₁ to C₆ carbonic acid.
 13. The electrolyte composition of claim 12 wherein R¹ and R² are a C₈ to C₁₂ alkyl side chain, R³ is a C₁ to C₃ alkyl side chain, R⁴ corresponds to the general formula [CH₂—CH₂—O]_(n)H with n=1 to 5, and X⁻ is the anion of a C₂ to C₄ carbonic acid.
 14. The electrolyte composition of claim 12 wherein R¹ and R² are a C₁₀ alkyl side chain, R³ is a C₁ alkyl side chain, R⁴ corresponds to the general formula [CH₂—CH₂—O]_(n)H with n=1 to 5, and X⁻ is the anion of a C₂ to C₄ carbonic acid.
 15. The electrolyte composition of claim 12 wherein the average molecular weight of the wetting agent is between about 200 and about 1000 g/mol.
 16. The electrolyte composition of claim 12 wherein the average molecular weight of the wetting agent is between about 400 and about 500 g/mol.
 17. The electrolyte composition of claim 1 further comprising polytetrafluorethylene particles with an average particle diameter of about 10 to about 1000 nm.
 18. The electrolyte composition of claim 1 further comprising polytetrafluorethylene particles with an average particle diameter of about 100 to about 300 nm.
 19. The electrolyte composition of claim 18 wherein the electrolyte contains the polytetrafluorethylene particles at a concentration of 0.1 to 1000 mg/l.
 20. The electrolyte composition of claim 18 wherein the electrolyte contains the polytetrafluorethylene particles at a concentration of about 0.5 to 5 mg/l.
 21. A process for the electrolytic deposition of a matt metal layer on a substrate comprising immersing the substrate in the electrolytic composition of claim 1 and applying a current between the substrate and the counter electrode. 